KR101049675B1 - Method for producing a modified conjugated diene polymer, a composition comprising the polymer and a tire comprising the composition - Google Patents

Abstract

The present invention has an object to provide a conjugated diene-based polymer, subjected to a vulcanization treatment to make a vulcanized rubber, the vulcanized rubber useful as a material for tire treads excellent in the balance among wet skid characteristics, low hysteresis loss, abrasion resistance, breaking strength and rigidity, and to provide its manufacturing process. According to the present invention, there is provided the process for manufacturing a modified conjugated diene-based polymer having a modifying group in its molecule, the process including a step of obtaining a conjugated diene-based polymer by polymerizing a conjugated diene compound, or a conjugated diene compound and an aromatic vinyl compound, by using an alkaline metal-based initiator or an alkaline earth metal-based initiator in a hydrocarbon solvent, and a step of reacting active terminals of the polymer with a glycidylamino group-containing low molecular compound having two or more tertiary amino groups and three or more glycidyl groups bonded to the amino groups in a molecule of the compound, and an oligomer of a dimmer or more of the low molecular compound as modifying agents, wherein the reaction is performed using 75 to 95% by mass of the low molecular compound and 25 to 5% by mass of the oligomer based on the total amount of the modifying agents.

Description

Process for producing a modified conjugated diene-based polymer, a composition comprising the polymer and a tire comprising the composition TECHNICAL FIELD

The present invention relates to a process for producing the modified conjugated diene polymer. More specifically, the present invention relates to a method for producing a conjugated diene-based polymer having a modifying group using a specific polyfunctional compound in a molecule, a composition comprising a polymer obtained by the production method, and a tire comprising the composition.

According to the recent demand for low fuel consumption for automobiles, there is a demand for conjugated diene-based polymers in which vulcanized rubbers with low rolling resistance, excellent wear resistance and fracture characteristics, excellent wet skid resistance, and high rigidity are obtained as rubber materials for tires. It is becoming.

In order to reduce the rolling resistance of the tire, it is necessary to reduce the hysteresis loss of the vulcanized rubber. As an evaluation index of hysteresis loss, a rubber material having a high resilience of 50 to 80 ° C., a tan δ of 50 to 80 ° C. or a good good heat generation is preferable. Natural rubber, polyisoprene rubber, polybutadiene rubber, and the like are known as rubber materials with low hysteresis loss, but these have a problem of low wet skid resistance.

As a method of reducing hysteresis loss without impairing wet skid resistance, in the styrene-butadiene (co) polymer of various structures polymerized by an organolithium initiator in a hydrocarbon solvent, the 1,2-vinyl structure of the microstructure of butadiene The method of making high, the method of introduce | transducing a modifying group in a polymer terminal, etc. are proposed.

On the other hand, in order to improve the steering stability of high-performance tires, the stiffness of the vulcanized rubber is required to be high, and the evaluation index is that the change of the storage elastic modulus at 50 ° C. is small and the storage elastic modulus at the high strain is high. desirable. As a method of increasing the stiffness of the vulcanized rubber, there was no effective method except for improving the filler composition except for increasing the molecular weight as an improvement in the raw material rubber.

Under such circumstances, for example, Patent Documents 1 to 4 describe active ends of rubbery polymers,

A modified polymer obtained by reacting a polyfunctional low molecular weight compound having an epoxy group and a tertiary amino group in a molecule is disclosed.

Patent Document 1: Japanese Patent No. 2538629

Patent Document 2: International Publication No. 01/23467

Patent Document 3: Japanese Patent Application Laid-Open No. 2001-131227

Patent Document 4: Japanese Patent Application Laid-Open No. 2003-119223

[Initiation of invention]

[Problem to Solve Invention]

However, in the above-mentioned prior art, although the balance of hysteresis loss and wet skid resistance is improved by the vulcanized rubber composition using these polymers, rigidity and abrasion resistance are not enough, and improvement is desired.

In view of these circumstances, the present invention is excellent in the balance of wet skid characteristics, low hysteresis loss resistance, abrasion resistance, and fracture strength when the reinforcing filler is blended and vulcanized to form vulcanized rubber. It is providing the manufacturing method of the polymer from which a vulcanized rubber is obtained.

[Means for solving the problem]

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, the present inventors discovered the manufacturing method of the conjugated diene type polymer by which the high performance vulcanized rubber composition is obtained by making the active terminal of a polymer react with a specific polyfunctional compound as a modifier, and completes this invention. Reached.

That is, in the present invention, when producing a modified conjugated diene-based polymer having a modified group in a molecule, a method of generally reacting the active terminal of the polymer with a glycidylamino group-containing low molecular compound as a modifier has been carried out. It was thought that the method of making the oligomer react more than a sieve is not preferable because of the fall of the modification rate by the fall of the hydroxyl group, epoxy equivalent, etc. which an oligomer has. The present invention is excellent in the balance of wet skid characteristics, low hysteresis loss, wear resistance, and breaking strength, which is the object of the present invention, by reacting the active terminal of a specific polymer with a glycidylamino group-containing low molecular weight compound and an oligomer thereof as a modifier at a specific ratio. The present invention has been found to provide a method for producing a modified conjugated diene-based polymer from which a vulcanized rubber having excellent rigidity can be obtained.

The present invention

[1] A method for producing a modified conjugated diene polymer having a modifying group in a molecule,

Obtaining a conjugated diene polymer by polymerizing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound in an hydrocarbon solvent using an alkali metal initiator or an alkaline earth metal initiator;

Reacting the active terminal of the polymer with a glycidylamino group-containing low molecular compound having two or more tertiary amino groups and three or more glycidyl groups bonded to the amino group as a modifier, and an oligomer or more of a dimer of the low molecular compound A step of causing the reaction to react with 75 to 95% by mass of the low molecular weight compound and 25 to 5% by mass of the oligomer with respect to the total amount of the modifier.

Method for producing a modified conjugated diene-based polymer, including

[2] The method for producing a modified conjugated diene polymer according to the above [1], which is reacted using a low molecular compound having two diglycidylamino groups in a molecule as the low molecular compound.

[3] The method for producing the modified conjugated diene polymer according to the above [1] or [2], wherein the conjugated diene polymer is at least one random copolymer of a conjugated diene compound and an aromatic vinyl compound.

[4] a modified conjugated diene-based polymer obtained by the method according to any one of the above [1] to [3],

[5] 100 parts by mass of the modified conjugated diene polymer described in the above [4];

5 to 60 parts by mass of extender oil having 3% by mass or less of polycyclic aromatic components by IP346 method

Comprising a dielectric modified conjugated diene-based polymer composition,

[6] a modified conjugated diene polymer composition comprising 100 parts by mass of the modified conjugated diene polymer described in the above [4] and 1 to 200 parts by mass of a silica-based inorganic filler;

[7] a modified conjugated diene-based polymer composition comprising 100 parts by mass of the modified conjugated diene-based polymer according to the above [4] and 1 to 100 parts by mass of carbon black;

[8] A tire comprising the composition according to the above [6] or [7]

To provide.

[Effects of the Invention]

According to the production method of the present invention, when a reinforcing filler is blended and vulcanized to form a vulcanized rubber, the vulcanized rubber is excellent in the balance of wet skid characteristics, low hysteresis loss resistance, abrasion resistance, and breaking strength and is excellent in rigidity. It is obtained and becomes a rubber composition suitable for rubber | gum for a tire, dustproof rubber, shoes, etc. In particular, when the reinforcing filler is precipitated silica or precipitated silica and carbon black, the effect is remarkable.

1 shows GPC of denaturant A used in the present embodiment.

2 shows the GPC of the denaturant B used in the present embodiment.

3 shows a calibration curve by standard polystyrene of GPC used in this embodiment.

4 shows the mass spectrum of the denaturant A used in the present embodiment.

5 shows the mass spectrum of the denaturant B used in the present embodiment.

BEST MODE FOR CARRYING OUT THE INVENTION [

EMBODIMENT OF THE INVENTION Hereafter, the best form (henceforth "this embodiment") for implementing this invention is demonstrated in detail. In addition, this invention is not limited to the following embodiment, It can variously deform and implement within the range of the summary.

The present embodiment is a method of producing a modified conjugated diene polymer having a modified group in a molecule, wherein a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound are polymerized in an hydrocarbon solvent using an alkali metal initiator or an alkaline earth metal initiator. Then, 75-95 mass% of glycidylamino group containing low molecular compounds which have the active terminal of this polymer, and two or more tertiary amino groups and 3 or more glycidyl groups couple | bonded with these amino groups in a molecule as a modifier, and the said low molecular weight compound It is a manufacturing method of the modified conjugated diene type polymer which makes 25-5 mass% of oligomers more than a dimer of react. In addition, content of the oligomer which consists of a low molecular weight compound and its low molecular weight compound is shown by the mass% with respect to a modifier whole quantity. In addition, the term "modified group" used in this embodiment means group which reacts with another chemical substance. In particular, in this embodiment, as a specific modification group, an amino group, an epoxy group, a hydroxyl group, a carbonyl group, etc. are mentioned.

As the alkali metal initiator or alkaline earth metal initiator used in the production method of the present embodiment, all alkali metal initiators or alkaline earth metal initiators having the ability to initiate polymerization can be used. Especially, at least 1 sort (s) of compound chosen from the group which consists of an organoalkali metal compound and an organoalkali earth metal compound is used preferably. As an organoalkali metal compound, an organolithium compound is especially preferable. As an organolithium compound, a low molecular weight thing, an organolithium compound of a solubilized oligomer, further having lithium alone in one molecule, having a plurality of lithium in one molecule, and a carbon-lithium bond in a bonding mode of an organic group and lithium And a nitrogen-lithium bond, a tin-lithium bond, and the like. Specific examples of the mono organolithium compound include, but are not limited to, the following: n-butyllithium, sec-butyllithium, tert-butyllithium, n-hexyllithium, benzyllithium, phenyllithium, stilbenlithium, and the like. have. Examples of the polyfunctional organolithium compound include, but not limited to the following, tetramethylenedilithium, a reactant of sec-butyllithium and diisopropenylbenzene, 1,3,5-tririthiobenzene, n-butyllithium and 1, The reactant of 3-butadiene and divinylbenzene, the reactant of n-butyllithium and a polyacetylene compound, etc. are mentioned. Moreover, as a compound which consists of a nitrogen-lithium bond, it is not limited to the following, Dimethyl amino lithium, dihexyl amino lithium, diisopropyl amino lithium, hexamethylene imino lithium, etc. are mentioned. Furthermore, the organoalkali metal compound disclosed in US Patent 5,708,092 specification, UK Patent 2,241,239 specification, US Patent 5,527,753 specification, etc. can also be used.

Particularly preferred as the organolithium compound used in the present embodiment are n-butyllithium and sec-butyllithium. These organolithium compounds are used not only as one kind but also as a mixture of two or more kinds.

Examples of other organic alkali metal compounds include, but are not limited to, organic sodium compounds, organic potassium compounds, organic rubidium compounds, organic cesium compounds, and the like. Specific examples include, but are not limited to, sodium naphthalene and potassium naphthalene, and lithium, sodium, potassium alkoxides, sulfonates, carbonates, amides, and the like. Moreover, it may be used in combination with another organometallic compound.

In addition, as an alkaline earth metal compound, it is not limited to the following, An organic magnesium compound, an organic calcium compound, and an organic strontium compound are typical. Although it does not specifically limit to the following, Dibutyl magnesium, ethyl butyl magnesium, propyl butyl magnesium, etc. are mentioned. In addition, compounds such as alkoxides, sulfonates, carbonates, and amides of alkaline earth metals are used. These organic alkaline earth metal compounds may be used in combination with an organoalkali metal-based initiator and other organometallic compounds.

The conjugated diene polymer obtained in the production method of the present embodiment is a polymer obtained by polymerization with the alkali metal initiator and / or alkaline earth metal initiator described above, and grown by anionic polymerization, and the polymerization is batch or one reactor or two. In a polymerization mode such as continuous in two or more connected reactors.

It is preferable that the conjugated diene type polymer obtained by the manufacturing method of this embodiment is a polymer which has an active terminal especially obtained by the growth reaction by living anion polymerization.

Examples of the conjugated diene polymer produced in the production method of the present embodiment include polymers of conjugated diene compounds, copolymers of conjugated diene compounds, and copolymers of conjugated diene compounds and aromatic vinyl compounds. In the polymerization reaction of the present embodiment, for the purpose of randomly copolymerizing the aromatic vinyl compound with the conjugated diene compound, it is also possible to add a small amount of the polar compound as the vinylating agent. Examples of the polar compound include, but are not limited to, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, Ethers such as 2,2-bis (2-oxolanyl) propane and the like; Tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidin and the like; Alkali metal alkoxide compounds such as potassium-t-amylate, potassium-t-butyrate, sodium-t-butyrate, sodium-t-amylate and the like; Phosphine compounds such as triphenylphosphine and the like; Alkyl or arylsulfonic acid compounds, etc. are used. These polar compounds can be used individually or in combination of 2 types or more, respectively.

The amount of the polar compound to be used is selected according to the purpose and the degree of effect. Usually, it is 0.01-100 mol with respect to 1 mol of initiators. Such a polar compound (vinylating agent) can be used in an appropriate amount depending on the desired amount of vinyl bonds as a microstructural regulator of the polymer diene moiety. Most polar compounds have an effective randomization effect in the copolymerization of a conjugated diene compound and an aromatic vinyl compound and can be used as an agent for adjusting the distribution of the aromatic vinyl compound and the amount of styrene block.

The method of randomization may be a method of intermittently adding a part of 1.3-butadiene during the copolymerization, as described in JP-A-59-140211.

Specific examples of the conjugated diene compound used in the present embodiment include, but are not limited to, the following, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1 , 3-pentadiene, 1,3-heptadiene, 1,3-hexadiene, and the like, and the like, and may be used alone or in combination of two or more thereof. Preferable compounds of the conjugated diene compound used in the present embodiment include 1,3-butadiene and isoprene.

In addition, examples of the aromatic vinyl compound used in the present embodiment include, but are not limited to the following, styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, diphenylethylene, and the like. , 1 type, or 2 or more types are used in combination. Styrene is mentioned as a preferable compound of the aromatic vinyl compound used by this embodiment. In order to prevent cold flow of the conjugated diene polymer, a polyfunctional aromatic vinyl compound such as divinylbenzene can also be used from the viewpoint of controlling the branching. When the molecular weight (weight average molecular weight: polystyrene conversion by gel permeation chromatography (GPC) method) of the conjugated diene polymer manufactured in the manufacturing method of this embodiment is considered, workability and physical property are 100,000-100 million, and are preferable.

Although the hydrocarbon solvent used in the manufacturing method of this embodiment is not limited to the following, A saturated hydrocarbon, an aromatic hydrocarbon, etc. are mentioned, Aliphatic hydrocarbons, such as butane, a pentane, hexane, a pentane, heptane; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane; Hydrocarbons consisting of aromatic hydrocarbons such as benzene, toluene and xylene and mixtures thereof are used. The conjugated diene compound, the aromatic vinyl compound, and the hydrocarbon solvent used in the present embodiment each have a high concentration of active terminals by treating an arene or acetylene, which is an impurity, with an organometallic compound before providing each of the mixed solution to the polymerization reaction alone or separately. It is possible to obtain a polymer having the above, and to achieve a high modification rate.

In order to exert the excellent effect of the present embodiment in particular, the ratio of the polymer having a functional group component, that is, the modification ratio is preferably 5% by weight or more, more preferably 20% by weight or more by the production method of the present embodiment. It is preferable to manufacture the modified conjugated diene polymer (Hereinafter, it may only be called "modified conjugated diene polymer.") Which has a modified group. As a quantitative method of polymer which has a functional group component, it can measure by chromatography which can separate a functional group containing modified component and a non-modified component. As a method of this chromatography, the method of quantifying by using the internal standard of a non-adsorbing component for comparison using the GPC column which used the silica which adsorb | sucks a functional group component as a filler is preferable.

Although the conjugated diene type polymer obtained by the manufacturing method of this embodiment is not limited to the following as a random copolymer, Butadiene-isoprene random copolymer, butadiene-styrene random copolymer, isoprene-styrene random copolymer, butadiene- Isoprene-styrene random copolymers and the like. Examples of the random copolymer include a completely random copolymer close to the statistical random composition, a tapered random copolymer having a distribution in the composition in a tapered shape, and the like. In addition, even a homopolymer having a single monomer composition may be a polymer having a uniform composition by its monomer bonding mode, i.e., 1,4 bond and 1,2 bond, or the like, or have a distribution in the composition, or have a block form (having a block bond), Various structures are possible.

As a block bond, the thing which the homopolymer block couple | bonded, the block containing the random polymer couple | bonded, the block containing the taper random polymer couple | bonded, etc. are mentioned. There are also two type block copolymers consisting of two, three type block copolymers consisting of three, four type block copolymers consisting of four, and the like. As an example of the block polymer, a block containing an aromatic vinyl compound such as styrene is S, a block containing a conjugated diene compound such as butadiene or isoprene and / or a block containing a copolymer of an aromatic vinyl compound and a conjugated diene compound. When B is represented by B, there are S-B2 type block copolymers, SB-S3 type block copolymers, SBS-B4 type block copolymers, block copolymers represented by (SB) mX, and the like.

As an example of a block polymer, the structure represented by the following general formula is mentioned more generally, for example.

(S-B) n, S- (B-S) n, B- (S-B) n, [(S-B) n] m-X, [(B-S) n-B] m-X, [(S-B) n-S] m-X

(In the above formula, the boundary of each block does not necessarily need to be clearly distinguished, and when the block B is a copolymer of an aromatic vinyl compound and a conjugated diene compound, the aromatic vinyl compound in the block B is uniformly distributed, or The taper may be distributed in a tapered shape, and in the block B, a plurality of portions in which the aromatic vinyl compound is uniformly distributed and / or in a tapered shape may be present in plural numbers, and the block B may contain an aromatic vinyl compound content. A plurality of different segments may coexist, n is an integer of 1 or more, preferably an integer of 1 to 5, m is an integer of 2 or more, preferably an integer of 2 to 11, and X is a coupling agent. When the residue or residue of a polyfunctional initiator is shown and there exist two or more blocks S and B in a copolymer, these are these, Structure, such as molecular weight and composition may be the same or different and can also be of a polymer chain structure which bond to X may be the same or different). In the present embodiment, any mixture of those having a structure represented by the above formula may be used.

In this embodiment, all or part of a double bond can be converted into a saturated hydrocarbon by hydrogenating the modified conjugated diene type polymer which has a modifying group further in an inert solvent. In that case, heat resistance and weather resistance can be improved, and deterioration of the product at the time of processing at high temperature can be prevented, and also the mobility of a molecule | numerator can be changed, or compatibility with other high molecular compounds can be improved. As a result, it exhibits excellent performance in various applications such as automobile use.

More specifically, in this embodiment, the hydrogenation rate (namely, hydrogenation rate) of the unsaturated double bond based on a conjugated diene compound can be arbitrarily selected according to the objective, and is not specifically limited. When obtaining a polymer having good heat aging resistance and weather resistance, it is more than 70% of the unsaturated double bond based on the conjugated diene compound in the polymer, preferably 75% or more, more preferably 85% or more, particularly preferably 90 It is preferable that% or more are hydrogenated. Moreover, in order to improve thermal stability, molecular motility, or compatibility with resin, the hydrogenation rate in a polymer is 3 to 70% is preferable, More preferably, it is 5 to 65%, More preferably, it is 10 to 60%. The hydrogenation rate of the aromatic double bond based on the aromatic vinyl compound in the copolymer of the conjugated diene compound and the aromatic vinyl compound is not particularly limited, but the hydrogenation rate is 50% or less, preferably 30% or less, more preferably. Preferably it is 20% or less. The hydrogenation rate can be calculated | required by a nuclear magnetic resonance apparatus (NMR).

As a method of hydrogenation, a well-known method can be used. In particular, the preferred method of hydrogenation is a method of hydrogenating by blowing gaseous hydrogen into the polymer solution in the presence of a catalyst. Examples of the catalyst include a catalyst in which a noble metal is supported on a porous inorganic material as a heterogeneous catalyst, a catalyst in which salts such as nickel and cobalt are solubilized and reacted with organic aluminum as a homogeneous catalyst, a catalyst using metallocene such as titanocene, and the like. Can be. Among these, the titanocene catalyst which can select especially mild hydrogenation conditions is preferable. In addition, hydrogenation of an aromatic group is possible by using the supported catalyst of a noble metal.

Although it is not limited to the following as a specific example of a hydrogenation catalyst,

(1) a supported heterogeneous hydrogenation catalyst in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, and the like;

(2) what is called a Ziegler-type hydrogenation catalyst which uses transition metal salts, such as organic acid salts, such as Ni, Co, Fe, Cr, or an acetylacetone salt, and a reducing agent, such as organic aluminum;

(3) so-called organometallic complexes such as organometallic compounds such as Ti, Ru, Rh, and Zr;

Etc. can be mentioned. For example, Japanese Patent Laid-Open No. 42-8704, Japanese Patent Laid-Open No. 43-6636, Japanese Patent Laid-Open No. 63-4841, and Japanese Patent Laying-Open No. 1 as hydrogenation catalysts The hydrogenation catalyst of -37970, Unexamined-Japanese-Patent No. 1-53851, Unexamined-Japanese-Patent No. 2-9041, and Unexamined-Japanese-Patent No. 8-109219 can be used. As a preferable hydrogenation catalyst, the reaction mixture of a titanocene compound and a reducing organometallic compound is mentioned.

In the manufacturing method of this embodiment, after superposing | polymerizing the said conjugated diene compound or the said conjugated diene compound, and the said aromatic vinyl compound, the active terminal of the obtained polymer and two or more tertiary amino groups in the molecule were couple | bonded with these amino groups. 75-95 mass% of glycidylamino group containing low molecular weight compounds which have three or more glycidyl groups, and 25-5 mass% of oligomers more than the dimer of the said low molecular weight compound are made to react. Here, content of the oligomer which consists of a low molecular weight compound and its low molecular weight compound shows the mass% with respect to modifier whole quantity.

The low molecular weight compound used in the present embodiment is a glycidylamino group-containing low molecular compound having two or more tertiary amino groups and three or more glycidyl groups bonded to these amino groups in the molecule, and two or more diglycidylamino groups in the molecule. The low molecular weight compound which has, and the low molecular weight compound which has one diglycidyl amino group and one or more monoglycidyl amino group in a molecule | numerator are contained. As a low molecular weight compound, it is preferable to use the low molecular weight compound which has two diglycidyl amino groups in a molecule | numerator. In this embodiment, it is more preferable that the low molecular weight compound is an organic compound whose molecular weight is 1000 or less.

As for the low molecular weight compound used by this embodiment, the preferable molecular structure of the low molecular weight compound which has two diglycidyl amino groups in a molecule | numerator is represented by General formula (1).

In Formula 1, R has a bivalent hydrocarbon group or at least 1 polar group chosen from nitrogen, such as oxygen, such as an ether, an epoxy, a ketone, sulfur, such as a thioether, and a thioketone, a tertiary amino group, and an imino group. It is a divalent organic group. As a bivalent hydrocarbon group, it is a saturated, unsaturated linear, branched, cyclic hydrocarbon which may contain an alkylene group, an alkenylene group, a phenylene group, etc. Specific examples include methylene, ethylene, butylene, cyclohexylene, 1,3-bis (methylene) -cyclohexane, 1,3-bis (ethylene) -cyclohexane, o-, m-, p- Phenylene, m-, p-xylene, bis (phenylene) -methane, etc. are mentioned.

As a low molecular weight compound used by this embodiment, Preferably, there is little or no active hydrogen, such as a hydroxyl group, a carboxyl group, a primary and a secondary amino group.

Although the specific example of the low molecular weight compound used by this embodiment is not limited to the following, 1, 3-bis (N, N- diglycidyl aminomethyl) cyclohexane, N, N, N ', N'-tetra Glycidyl-m-xylenediamine, 4,4-methylene-bis (N, N-diglycidylaniline), 1,4-bis (N, N-diglycidylamino) cyclohexane, N, N , N ', N'-tetraglycidyl-p-phenylenediamine, 4,4'-bis (diglycidylamino) benzophenone, 4- (4-glycidylpiperazinyl)-(N, N -Diglycidyl) aniline, 2- [2- (N, N-diglycidylamino) ethyl] -1-glycidylpyrrolidine, and the like. Among these, 1,3-bis (N, N- diglycidylaminomethyl) cyclohexane and the like are particularly preferable.

The modifying agent used in the present embodiment is a low molecular weight compound, a reactant of polyamine and epichlorohydrin, and a condensation product of polyamine and epichlorohydrin as an oligomer or higher oligomer of the low molecular weight compound. In addition to the dimer or higher oligomers resulting from the reaction of two molecules of amines with one molecule of epichlorohydrin, in the presence of hydrochloric acid, the epoxy groups of the glycidyl group of the low molecular compound react with each other, and these reactions are complexed. Oligomers of more than the dimers produced are included. Moreover, it is also obtained by the coupling reaction of epoxy groups by an acid and an alkali.

When these oligomers are obtained by the side reaction of reaction at the time of manufacturing a glycidylamino group containing low molecular weight compound, it produces | generates also by the ratio, temperature, and concentration of a reactant, and also under the storage conditions of a glycidyl compound. On the other hand, it is possible to reduce the amount of oligomer from the mixture containing the oligomer by methods such as vacuum distillation and solvent extraction.

As an oligomer used by this embodiment, it is the range of a dimer thru | or a tetramer. As an example of the component of the oligomer used by this embodiment, the dimer of following formula (2) and the trimer of following formula (3) are shown.

In addition, R in the said chemical formula is the same definition as the above-mentioned.

In addition, the molecular weight of said Formula (2) and (3) make M molecular weight of a low molecular weight compound, and in the case of n-mer, it becomes nM-56 (n-1). The modifier used in the present embodiment is a mixture of a low molecular weight compound and an oligomer component thereof, and is preferably reacted with the active terminal of the polymer.

In the manufacturing method of this embodiment, 75-95 mass% of glycidylamino group containing low molecular weight compounds and 25-5 mass% of oligomers of the dimer of the said low molecular weight compound are made to react with the active terminal of a polymer. In the range of the low molecular weight compound and the oligomer in the above range, a vulcanized rubber having excellent balance of wet skid property, low hysteresis loss resistance, abrasion resistance, and breaking strength, which is an effect of the present invention, and excellent rigidity is obtained. In particular, when the oligomer component is reduced within the range and the glycidylamino group-containing low molecular weight compound is 85 to 95 mass%, and the oligomer or higher oligomer of the low molecular weight compound is 15 to 5 mass%, the wet skid is maintained while maintaining high rigidity. A vulcanized rubber having a better balance of characteristics and low hysteresis loss is obtained. On the other hand, when the oligomer component is increased, a vulcanized rubber having superior rigidity is maintained while maintaining a balance of wet skid characteristics and low hysteresis loss. When the glycidylamino group-containing low molecular compound 77 mass% or more and 93 mass% or less and the dimer or more oligomer of the low molecular compound 7 mass% or more and 23 mass% or less are reacted, these balances obtain a more preferable effect.

The ratio of the low molecular weight compound to the oligomer component is measured by GPC, and is determined by selecting a column capable of appropriately measuring the low molecular weight compound to the oligomer component according to a conventional method. As the amount of the oligomer component, the slope between the low molecular compound peak and the minimum molecular weight oligomer peak in the polymer observation portion of the low molecular compound peak by GPC changes to the point where the component peak on the polymer side becomes zero, or Using the polystyrene equivalent molecular weight, the total amount of the oligomer component is calculated using the upper limit of the molecular weight up to 10 times the molecular weight of the glycidylamino group-containing low molecular weight compound, and the ratio with the integrated amount of the peak area of the low molecular weight compound is%. Represented by

In the manufacturing method of this embodiment, it is preferable that the reaction ratio of the active terminal of a conjugated diene type polymer, and a modifier reacts the glycidyl group of a modifier at least 0.2 mol with respect to an active terminal. As an upper limit, it is about 10 mol as an quantity which an effect is not expected even if it puts in more. In the modified conjugated diene-based polymer obtained in the present embodiment, the proportion of the polymer that the modified group has in the molecule is preferably 20 to 80 mass% of the whole. In that case, the excellent performance which is the objective of this invention is obtained. The proportion of the polymer that the denaturant has in the molecule depends on the living ratio of the polymer before modification, that is, the rate at which the active end is alive and the amount of the modifier used. As for the modified conjugated diene type polymer obtained by this embodiment, 200,000-2 million are preferable in weight average molecular weight. In that case, the balance between workability and physical properties is good. In this embodiment, 300,000-2 million are more preferable. The modified conjugated diene polymer obtained in the present embodiment is preferably a conjugated diene polymer obtained by a continuous polymerization method, a molecular weight distribution is monomodal, and a modified conjugated diene polymer having Mw / Mn of 1.8 to 3 is preferable. Moreover, it is more preferable to set it as the modified conjugated diene type polymer whose Mw / Mn exceeds 2.1 and is 3 or less. In this range, the effect of the present invention is more remarkable. That is, the vulcanized rubber which is excellent in wear resistance and excellent in rigidity is obtained, maintaining the balance of wet skid property and low hysteresis loss property.

In this embodiment, the reaction terminator can be added to the solution of the inert solvent of the polymer which made the low molecular weight compound which has glycidylamino group, and this oligomer react as a modifier. As a reaction terminator, Alcohol, such as methanol, ethanol, a propanol normally; Organic acids such as stearic acid, lauric acid and octanoic acid; Water and the like are used.

In this embodiment, the metals contained in a polymer can be demineralized as needed. Usually, as a method of deliming, water, an organic acid, an inorganic acid, an oxidizing agent such as hydrogen peroxide or the like is brought into contact with the polymer solution to extract metals, and then a method of separating the aqueous layer.

In this embodiment, antioxidant can be added to the solution of the inert solvent of a polymer. As antioxidant, a phenol stabilizer, a phosphorus stabilizer, a sulfur stabilizer, an amine stabilizer, etc. are mentioned.

The method of acquiring a polymer from a polymer solution can be performed by a well-known method. For example, after the solvent is separated by steam stripping or the like, the polymer is separated by filtration and further dewatered and dried to obtain the polymer, concentrated in a flushing tank, and further devolatilized with a vent extruder, drum dryer. The method of devolatilizing directly, etc. can be employ | adopted.

One of the preferred embodiments of the present invention is a case where the conjugated diene polymer is a random copolymer. As a monomer, the living random copolymer of a conjugated diene compound and a styrene is obtained in an inert solvent using the organic monolithium compound as an initiator using the 1 type, or 2 or more types of conjugated diene compound, and a combination of styrene. The polymer has a glass transition temperature of −100 ° C. to 0 ° C., where the ratio of 1,4-bonds to 1,2 or 3,4 bonds of the conjugated diene portion is 10% to 90% versus 90% to 10%. The amount of bound styrene in the copolymer is 1 to 50 mass%. It is preferable that the chain distribution of styrene in a copolymer is random. In that case, the rubber excellent for the tire tread is obtained. As a random copolymer, since the chain structure of styrene is few, the amount of styrene insoluble components of the osmic acid decomposition product by the Korthoff method is 3 mass% or less per polymer. In addition, a completely random structure is more preferred. That is, isolated styrene (one unit of styrene) by the ozone decomposition method is 40 mass% or more of the total bound styrene, and chain styrene (the styrene is 8 or more continuous) is 5 mass% or less of the total bound styrene, Preferably it is 2.5 mass% or less.

The viscosity of the modified conjugated diene polymer obtained by the production method of the present embodiment is controlled according to the use and the purpose. Usually, as a raw material rubber for vulcanized rubber, it is controlled by Mooney viscosity (100 degreeC 1 + 4 minutes) 20-100. When the Mooney viscosity is high, it is usually oil-extended to extend the physical properties by considering the ease in the finishing process at the time of manufacture and improving the processability during kneading, the dispersibility of the filler, and the dispersibility. It is set as said range. As the extender oil, aromatic oils, naphthenic oils, paraffin oils, and polycyclic aromatic components which are DMSO extraction components by the IP346 method, that is, PCA 3 mass% or less of aromatic substitute oil are preferably used. Aromatic substitute oils include Treated Distillate Aromatic Extract (T-DAE), Mild Extract Solvent described in Kautschuk Gummi Kunststoffe 52 (12) 799 (1999). Solvate (MES)), and the like, Safety Residual Aromatic Extract (S-RAE) manufactured by Japan Energy Corporation. In that case, when it is set as the dielectrically modified conjugated diene polymer composition containing 5 to 60 mass parts of polycyclic aromatic components by IP346 method, ie, 3 mass% or less of extender oils by IP346 method, in 100 mass parts of the modified conjugated diene polymer of this embodiment. In addition to the excellent performance characteristic of the present invention, it is possible to obtain a vulcanized rubber which is also excellent in environmental measures. The amount of the extender oil is arbitrary, but is usually 5 to 60 parts by weight, preferably 20 to 37.5 parts by weight based on 100 parts by weight of the polymer.

Dispersion of the filler selected from the group consisting of silica-based inorganic fillers, metal oxides and metal hydroxides in the modified conjugated diene polymer obtained by the production method of the present embodiment results in fine dispersion, and as a result excellent effects in performance are obtained. Obtained. When used for vulcanized rubber applications such as automobile parts such as tires and anti-vibration rubber and shoes, silica-based inorganic fillers are preferably used as reinforcing agents, and synthetic silicic acid having a primary particle diameter of 50 nm or less is particularly preferable. As synthetic silicic acid, wet silica and dry silica are preferably used. Wet silica is also called synthetic hydrous silicic acid. In that case, the filler is quickly and uniformly dispersed by short kneading and finely dispersed and reproducibly dispersed, and the obtained physical properties are very desirable. In addition, synthetic silicates are also used.

As the reinforcing agent, carbon black can be used. Carbon black is not particularly limited, and for example, furnace black, acetylene black, thermal black, channel black, graphite and the like can be used. Among these, furnace black is particularly preferable.

The modified conjugated diene polymer obtained by the production method of the present embodiment is preferably used as a raw material rubber for vulcanized rubber compositions. In that case, it is preferable to use as a vulcanized rubber composition which mix | blended 1-200 weight part of silica type inorganic fillers and 1-100 weight part of carbon black individually or in combination with respect to 100 weight part of raw material rubbers. In that case, especially as an effect of this invention, the dispersibility of a silica is good, it is stable, and the performance of a vulcanized rubber is excellent. Specifically, when the silica-based inorganic filler and the carbon black are uniformly dispersed to form a vulcanized rubber, a rubber with little strain dependence on storage modulus can be obtained. In the use of tire treads, improvement of the balance of low cloud resistance and wet skid resistance and improvement of abrasion resistance, improvement of strength, rigidity, and the like, which are conventionally known, are also suitable for tire rubber, dustproof rubber, shoes, and the like. do. In particular, by using the modified conjugated diene-based polymer obtained by the production method of the present embodiment, a tire using the modified conjugated diene-based polymer composition containing a silica-based inorganic filler and / or carbon black has a desirable performance.

The modified conjugated diene-based polymer obtained by the production method of the present embodiment is used alone or as a raw material rubber by mixing with other rubbers as necessary. When used in combination with other rubbers, when the proportion of the modified conjugated diene polymer of the present embodiment is excessively small, the effect of the modification of the present invention is not sufficiently exhibited, which is not preferable. As other rubbers, for example, natural rubber, polyisoprene rubber, emulsion polymerization styrene-butadiene copolymer rubber, solution polymerization random SBR (5 to 50% by weight of bonded styrene, the amount of 1,2-vinyl bonds in the butadiene bonding unit portion 10) To 80%), high trans SBR (70 to 95% of 1,4-trans bonds in the butadiene bond unit portion), low cispolybutadiene rubber, high cispolybutadiene rubber, high transpolybutadiene rubber (butadiene bond unit portion 1,4-trans bond amount 70 to 95%), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, solution polymerization random styrene-butadiene-isoprene copolymer rubber, emulsion polymerization random styrene-butadiene-isoprene copolymer rubber, emulsion polymerization styrene -Acrylonitrile-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, high vinyl SBR-low vinyl SBR block copolymer rubber, and polystyrene- Block copolymers such as polybutadiene-polystyrene block copolymer and the like. These can be suitably selected according to a required characteristic.

As a raw material rubber component, when the modified conjugated diene type polymer of this embodiment and another rubber are used, the ratio of each component is 10-99: 90-1 by weight ratio normally, Preferably it is 20-90: 80-10 More preferably, it is the range of 30-80: 70-20. Moreover, as a rubber compounding agent, a reinforcing agent, a vulcanizing agent, a vulcanization accelerator, a vulcanization adjuvant, oil, etc. can also be used, for example.

Although it does not specifically limit as a vulcanizing agent, For example, Sulfur, such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur, etc .; Sulfur halides such as sulfur monochloride and sulfur dichloride; Organic peroxides, such as dicumyl peroxide and ditert butyl peroxide, etc. are mentioned. Among these, sulfur is preferable and powdered sulfur is particularly preferable. The compounding ratio of the vulcanizing agent is usually in the range of 0.1 to 15 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the rubber component.

Examples of the vulcanization accelerator include sulfenamide series, thiourea series, thiazole series, dithiocarbamic acid series and xanthogenic acid vulcanization accelerators. The compounding ratio of the vulcanization accelerator is usually in the range of 0.1 to 15 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the rubber component.

Although there is no restriction | limiting in particular as a vulcanization adjuvant, For example, stearic acid, a zinc oxide, etc. can be used.

As oil used as a compounding agent, extender oils, such as an aromatic type, a naphthenic type, a paraffin type, and a silicone type, are selected according to a use, for example. The amount of oil used is usually 1 to 150 parts by weight, preferably 2 to 100 parts by weight, more preferably 3 to 60 parts by weight per 100 parts by weight of the rubber component. When the amount of oil used is in the above range, the dispersion effect of the reinforcing agent, the tensile strength, the wear resistance, the heat resistance, and the like are balanced by high values.

The composition which uses the modified conjugated diene type polymer obtained by the manufacturing method of this embodiment as a rubber component is fillers, such as a calcium carbonate, clay, a talc, a microphone, an aluminum hydroxide, magnesium hydroxide, etc. according to a conventional method other than the said component; Amine- or phenol-based anti-aging agents; Ozone deterioration inhibitors; Silane coupling agents; Active agents such as diethylene glycol; Processing aids; Tackifiers; Other compounding agents, such as a wax, can contain a required amount, respectively.

The composition which uses the modified conjugated diene type polymer obtained by the manufacturing method of this embodiment as a rubber component is manufactured by mixing each said component using the well-known kneading machine for rubbers, for example, a roll, a Benbury mixer, etc.

In addition, the modified conjugated diene polymer of this embodiment is obtained by the manufacturing method of the modified conjugated diene polymer mentioned above. And since the polymer of this embodiment consists of such a structure, it has the outstanding effect as mentioned above.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely based on an Example. However, the present invention is not limited at all by these. In addition, the analysis of the sample in the Example was performed by the method shown below.

(1) amount of bound styrene

The sample was used as the chloroform solution, and the binding styrene amount (weight%) was measured by absorption of UV254nm by the phenyl group of styrene (The Shimadzu Corporation make: UV-2450).

(2) styrene chain

The osmic acid decomposition product by the Kortov method was carried out by precipitation of insoluble polystyrene corresponding to block polystyrene in methanol, the amount of insoluble styrene was quantified, and the amount of block styrene expressed as mass% per polymer.

In addition, the content of the styrene short chain of one styrene unit and the long styrene chain in which eight or more styrene units are continuous is determined according to the method of Tanaka et al. (Polymer, 22,1721 (1981)). After digestion with ozone, analysis was by gel permeation chromatography (GPC).

(3) microstructure of butadiene moiety

The sample was used as a carbon disulfide solution, the infrared spectrum was measured in the range of 600 to 1000 cm ^-1 using a solution cell, and the microstructure of the butadiene portion was obtained from the predetermined absorbance according to the formula of Humpton's method. Preparation: FT / IR-4100).

(4) Mooney viscosity The viscosity after 4 minutes was measured at 100 degreeC and 1 minute of preheating using the L-type rotor according to JISK6300-1.

(5) molecular weight and molecular weight distribution

Chromatograms were measured using GPC using three columns of polystyrene gels as fillers, and the molecular weight and molecular weight distribution were calculated by a calibration curve using standard polystyrene. Tetrahydrofuran (THF) was used as the eluent. The column used was a guard column; Toso TSKguardcolumn HHR-H, column; Toso TSKgel G6000HHR, TSKgel G5000HHR, TSKgel G4000HHR, oven temperature: 40 degreeC, THF flow rate 1.0 ml / min, the Tosoh Corporation make: HLC-8020, a detector; RI was used. Samples were measured by injecting 200 μl of 20 mg THF dissolved in 20 mg THF as narrow molecular weight distribution.

(6) denaturation rate

(5) using a sample solution containing a sample and a low molecular weight internal standard polystyrene molecular weight 5000 (polystyrene is not adsorbed) by applying the modified property of the modified component to the GPC column using the silica gel as a filler. GPC (Tosoh Co., Ltd .: HLC-8020) of a polystyrene gel of Tosoh Co., Ltd., silica column (guard column; DIOL 4.6 × 12.5 mm 5 μm, column; Zorbax PSM-1000S, PSM-300S, PSM-60S, oven temperature: 40 ° C, THF flow rate 0.5 ml / min.GPC (manufactured by Tosoh Corporation: CCP8020 series build-up GPC system; AS-8020, SD-8022, CCPS, CO-8020, RI-8021) The chromatogram was measured and based on the internal standard polystyrene peak, the adsorption amount to the silica column was measured from these differences, and the modification rate was calculated | required. Samples were measured by injecting 200 μL of 20 mg of THF with 5 mg of standard polystyrene with a narrow molecular weight distribution of 10 mg to wide. As a specific procedure, the total peak area of the chromatogram using the polystyrene column was set to 100, the sample peak area was set to P1, the peak area of the standard polystyrene was set to P2, and the entire peak area of the chromatogram using the silica column was determined. The sample peak area is set to P3 and the peak area of standard polystyrene is set to P4, and the modification ratio (%) is calculated as [1- (P2 × P3) / (P1 × P4)] × 100.

(7) Quantification of low molecular weight compound and oligomer component of denaturant

As a GPC column, TSKgel G3000HXL, copper G2000HXL, and copper G1000HXL were used, THF was used as the eluent, the Tosoh Corporation HLC-8220 GPC apparatus was used, the detector was RI, oven temperature 40 ° C, eluent flow rate 1.0 ml / min. , 200 μL of a 1.0 mg / ml THF solution was injected to measure GPC. In addition, the molecular weight was corrected with standard polystyrene.

(8) Structure specification of oligomer component

It carried out by the mass spectrum.

The sample was dissolved in THF, thoroughly mixed with the matrix (ditranol), then added dropwise to the sample plate, and after solvent evaporation, MALDI-TOF / MS measurement was performed.

Measuring conditions

Device: Shimadzu AXIMA CFR plus

Laser: nitrogen laser (337 nm)

Detector format: linear mode

Ion detection: positive ion (positive mode)

Number of accumulations: 500

Matrix: Ditranol 10 mg / mL THF solution

Sample: 1 mg / mL THF solution

Scan Range: m / z1 to 2000

Example 1

Method for producing modified conjugated diene polymer

It has a volume of 10 liters, has an inlet at the bottom and an outlet at the head, and connects two autoclaves with a stirrer and a jacket as a reactor in series, butadiene 20.1 / min, styrene 9.9 g / min, and cyclohexane Mix at 120 g / min. The mixed solution was passed through a dehydration column packed with activated alumina, n-butyllithium was mixed in a static mixer at a rate of 0.004 g / min in order to remove impurities, and then continuously supplied from the bottom of the first reactor. And continuously supplying 2,2-bis (2-oxolanyl) propane as a polar substance at a rate of 0.0216 g / min and n-butyllithium as a polymerization initiator from the bottom of the first reactor, respectively, at a rate of 0.011 g / min. The reactor internal temperature was kept at 95 ° C. The polymer solution was continuously extracted from the reactor head and fed to the second reactor. The temperature of the second reactor was maintained at 95 ° C, and a mixture of 89.9 mass% of tetraglycidyl-1,3-bisaminomethylcyclohexane (monomer) and 10.1 mass% of an oligomer component (hereinafter, "modifier A") was used as a modifier. ) Was continuously added as a 1000-fold dilution of cyclohexane at a rate of 0.009 g / min to perform a modification reaction. After extracting this polymer solution continuously from a reactor, continuously adding an antioxidant with a static mixer, and adding 37.5 mass parts of extender oils NC140 by Japan Energy company with respect to 100 mass parts of polymers to this polymer solution, it mixed, The solvent was removed to obtain the desired dielectric modified diene polymer. Let this be polymer sample PA. In addition, GPC of the used modifier A is shown in FIG. In addition, a calibration curve with standard polystyrene of GPC is shown in FIG. 3. In addition, the mass spectrum of the modifier A is shown in FIG. 4. The main components of the oligomer component of the modifying agent A were the formulas (2) and (3) described above, and R was 1,3-bis (methylene) -cyclohexane.

The extender oil NC140 by Japan Energy Corporation is a polycyclic aromatic component by the method of IP346, that is, an aromatic replacement oil of PCA 3% by mass or less.

The polymer sample PA had 33 mass% of bound styrene, 67 mass% of bound butadiene, and 34 mol% of 1,2-vinyl bonds, 27 mol% of 1,4-cis bonds, and 1,4 for the microstructure of the butadiene portion. -39 mol% of trans-bonds, styrene chains, the amount of block styrene by the Kortov method is 0 mass%, styrene short chains by ozone decomposition is 47 mass%, and 8 or more styrene units are continuous. The content rate of the styrene long chain was 1 mass%. The molecular weight distribution by GPC was monomodal, the weight average molecular weight was 800,000 in weight average molecular weight (Mw) of polystyrene conversion, and the molecular weight distribution (Mw / Mn) was 2.5. The modification rate measured using the adsorptive silica column was 48 mass%. The Mooney viscosity of the dielectric polymer was ML1 + 4 (100 ° C.) 67.

[Example 2]

Example 1 WHEREIN: The thing using 81.7 mass% of tetraglycidyl- 1, 3-bisaminomethyl cyclohexane (monomer), and 18.3 mass% of oligomer components as a modifier (henceforth "modifier B"). Except for the same, polymer sample PB was obtained. In addition, the modifier B used used the product generally marketed as an epoxy resin raw material. His GPC is shown in FIG. 2. In addition, a calibration curve with standard polystyrene of GPC is shown in FIG. 3. In addition, the mass spectrum of the modifying agent B is shown in FIG. 5. The main components of the oligomer component were the above-mentioned formulas (2) and (3), and R was 1,3-bis (methylene) -cyclohexane.

As for the polymer sample PB, 33 mass% of binding styrene, 67 mass% of binding butadiene, and the microstructure of a butadiene part are 34 mol% of 1,2-vinyl bonds, 27 mol% of 1,4-cis bonds, 1,4 -39 mol% of trans-bonds, styrene chains, the amount of block styrene by Kortov's method is 0 mass%, the styrene short chains by ozone decomposition is 47 mass%, and 8 or more styrene units are continuous. The content rate of the styrene long chain which was present was 1 mass%. The molecular weight distribution by GPC was monomodal, the weight average molecular weight was 800,000 in weight average molecular weight (Mw) of polystyrene conversion, and the molecular weight distribution (Mw / Mn) was 2.6. The modification rate measured using the adsorptive silica column was 46 mass%. The Mooney viscosity of the dielectric polymer was ML1 + 4 (100 ° C.) 65.

Comparative Example 1

In Example 1, a mixture using 96.0 mass% of tetraglycidyl-1,3-bisaminomethylcyclohexane (monomer) and 4.0 mass% of an oligomer component (hereinafter referred to as "modifier C") as a modifier. The same procedure was followed except that polymer sample PC was obtained. The denaturant C was obtained by removing the poorly soluble oligomer component by reprecipitation from the denaturant A using a cyclohexane solvent.

The polymer sample PC had 33 mass% of bound styrene, 67 mass% of bound butadiene, and 34 mol% of 1,2-vinyl bonds, 27 mol% of 1,4-cis bonds, and 1,4- of the microstructure of the butadiene portion. 39 mol% of trans-bonds, styrene chains, the amount of block styrene by Kortop's method is 0 mass%, styrene short chains by ozone decomposition is 47 mass%, and styrene in which 8 or more styrene units are continuous. The content rate of long chain was 1 mass%. The molecular weight distribution by GPC was monomodal, the weight average molecular weight was 810,000 in weight average molecular weight (Mw) of polystyrene conversion, and molecular weight distribution (Mw / Mn) was 2.4. The modification rate measured using the adsorptive silica column was 48 mass%. The Mooney viscosity of the dielectric polymer was ML1 + 4 (100 ° C.) 67.

Comparative Example 2

Example 1 WHEREIN: The thing using 71.5 mass% of tetraglycidyl- 1, 3-bisaminomethyl cyclohexane (monomer), and 28.5 mass% of oligomer components (henceforth "modifier D") as a modifier. The same procedure was followed except that polymer sample PD was obtained. The modifier D was used after 30 minutes by reacting a 1 mass% solution of the modifying agent B in cyclohexane with 0.8 parts by mass of n-butyllithium per 100 parts by mass of the modifying agent B at room temperature.

Polymer sample PD has 33 mass% of bound styrene, 67 mass% of bound butadiene, and the microstructure of the butadiene portion is 34 mol% of 1,2-vinyl bond, 27 mol% of 1,4-cis bond, 1,4- The amount of trans-bonds is 39 mol%, the styrene chain is 0 mass% of block styrene by the Kortov method, the styrene short chain by ozone decomposition is 47 mass%, and the styrene length of 8 or more styrene units. The content rate of the chain was 1 mass%. The molecular weight distribution by GPC was monomodal, the weight average molecular weight was 800,000 in weight average molecular weight (Mw) of polystyrene conversion, and the molecular weight distribution (Mw / Mn) was 2.7. The modification rate measured using the adsorptive silica column was 40 mass%. The Mooney viscosity of the dielectric polymer was ML1 + 4 (100 ° C.) 61.

Samples (Sample PA to Sample PD) shown in Table 1:

The rubber composition was obtained by the combination shown in Table 2 as a copolymer as a raw material rubber.

The kneading method was performed by the following method.

Raw material rubber, filler (silica and carbon black), using a hermetically sealed kneader (0.3 liter capacity) equipped with a temperature control device, under the conditions of 65% filling rate and rotor speed 50/57 rpm as kneading in the first stage, The organosilane coupling agent, oil, zinc oxide and stearic acid were kneaded. At this time, the temperature of the closed kneader was controlled to obtain a rubber composition at a discharge temperature (compound) at 155 to 165 ° C.

Subsequently, as a kneading | mixing of the 2nd step | paragraph, after cooling the compound obtained above to room temperature, the antioxidant was added and it knead | mixed again in order to improve dispersion of a silica. Also in this case, discharge temperature (blend) was adjusted to 155-160 degreeC by the temperature control of a kneader.

After cooling, sulfur and a vulcanization accelerator were kneaded with an open roll set at 70 ° C. as kneading in the third stage.

This was shape | molded, it vulcanized by the vulcanization press at 160 degreeC for predetermined time, and the physical property was measured. Physical property measurement results are shown in Table 1.

The measuring method of each physical property was implemented with the following method.

(1) combined rubber

About 0.2 gram of the compound after the completion of the second stage kneading was cut into a shape of about 1 mm on each side, and placed in a Harris basket (100 mesh gold mesh), and weighed. Thereafter, after immersion in toluene for 24 hours, it was dried, weighed, and the amount of rubber bound to the filler was calculated in consideration of the insoluble component, and the ratio of rubber bound to the filler relative to the amount of rubber in the original formulation was determined. .

(2) blended Mooney viscosity

According to JIS K6300-1, the viscosity after 4 minutes was measured at 130 degreeC and 1 minute of preheating using an L-type rotor.

(3) hardness

Hardness was measured by the durometer and type A by JISK6253.

(4) tensile test

Tensile strength, elongation, and tensile stress at 100% elongation (100% Mo) and tensile stress at 300% elongation (300% Mo) by using dumbbell type No. 3 by the tensile test method of JIS K6251. Was measured.

(5) Measurement of viscoelastic properties

Tan δ and modulus of elasticity (G ') were measured by changing the strain at a frequency of 10 Hz and each measurement temperature (0 ° C and 50 ° C) by a torsion method using an Ares viscoelastic tester manufactured by Leometrics Scientific.

The Payne effect (ΔG ′) was expressed as the difference between the minimum and maximum values at 0.1% to 10% strain. The smaller the Payne effect, the better the dispersibility of the filler such as silica.

In addition, the higher the Tanδ at low temperature (0 ° C), the better the wet skid (grip) performance, and the lower the Tanδ at high temperature (50 ° C), the lower the hysteresis loss, and the lower the rolling resistance of the tire, that is, the lower the fuel efficiency. .

In addition, the elasticity modulus (G ') in 3% of high temperature (50 degreeC) deformation | transformation was made into the index of rigidity.

(6) measurement of resilience

Repulsive elasticity was measured at 0 degreeC and 50 degreeC by the Lupeke-type repulsion elasticity test method by JISK6255.

(7) pyrogenic

A Goodrich flexometer was used to express the difference between the rotational speed 1800 rpm, the stroke 0.225 inch, the load 55 pounds, the measurement start temperature of 50 ° C., and the start temperature after 20 minutes.

(8) Akron wear

Abrasion resistance was measured using an Akron abrasion tester at a load of 6 pounds and 3000 revolutions. The higher the index, the less wear and the better.

As shown in Examples 1 to 2 of Table 1, the modified conjugated diene-based polymer prepared according to the present embodiment has an increased amount of bonding rubber in the silica blend composition, resulting in a Payne effect (50 ° C ΔG '). It is small in size, excellent in dispersibility of silica, low temperature δδ, low hysteresis loss, and low tire resistance, that is, low fuel efficiency. Moreover, the balance of low fuel consumption and wet skid (grip) performance (Tanδ of low temperature) is excellent. Moreover, abrasion resistance is also favorable, the storage elastic modulus at high temperature is also high, and it is excellent in rigidity.

Although this embodiment was described in detail with reference to the specific embodiment, it is clear for those skilled in the art that various changes and correction can be added without deviating from the mind and range of this invention.

This application is based on the JP Patent application (Japanese Patent Application No. 2007-084310) of an Japan Patent Office on March 28, 2007, The content is taken in here as a reference.

The modified conjugated diene-based polymer produced by the production method of the present invention is used for compounding including reinforcing silica and various fillers, and thus has excellent strength characteristics, fuel economy, grip performance, wear resistance, and rigidity, and is suitable for tire treads. Vulcanized rubber compositions are provided. Moreover, it has industrial applicability, such as a tire use, shoe use, various auto parts, and industrial goods.

Claims (9)

As a manufacturing method of the modified conjugated diene type polymer which has a modified group in a molecule | numerator, Obtaining a conjugated diene polymer by polymerizing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound in an hydrocarbon solvent using an alkali metal initiator or an alkaline earth metal initiator; Reacting the active terminal of the polymer with a glycidylamino group-containing low molecular compound having two or more tertiary amino groups and three or more glycidyl groups bonded to the amino group as a modifier, and an oligomer or more of a dimer of the low molecular compound A step of causing the reaction to react with 75 to 95% by mass of the low molecular weight compound and 25 to 5% by mass of the oligomer with respect to the total amount of the modifier. A method for producing a modified conjugated diene-based polymer comprising a. The method for producing a modified conjugated diene polymer according to claim 1, wherein the low molecular weight compound is reacted with a low molecular weight compound having two diglycidylamino groups in a molecule. The method for producing a modified conjugated diene polymer according to claim 1, wherein the conjugated diene polymer is at least one random copolymer of a conjugated diene compound and an aromatic vinyl compound. The modified conjugated diene polymer obtained by the manufacturing method of any one of Claims 1-3. 100 parts by mass of the modified conjugated diene polymer according to claim 4, 5 to 60 parts by mass of extender oil having 3% by mass or less of polycyclic aromatic components by IP346 method A dielectric modified conjugated diene-based polymer composition comprising a. 100 parts by mass of the modified conjugated diene polymer according to claim 4, 1 to 200 parts by mass of silica-based inorganic filler A modified conjugated diene-based polymer composition comprising a. 100 parts by mass of the modified conjugated diene polymer according to claim 4, 1 to 100 parts by mass of carbon black A modified conjugated diene-based polymer composition comprising a. A tire comprising the composition of claim 6. A tire comprising the composition of claim 7.

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